Rubber chemical and use thereof



United States This invention relates to a new class of rubber chemicals and to utilization of these chemicals in rubber-filler mixtures whereby vulcanizates having improved physical properties are obtained.

The copending application of Brooks and Ewart, Serial No. 250,788, filed October 10, 1951, discloses that by incorporating the reaction products of organohalosilanes and polyhydric alcohols into uncured mixtures of rubber and certain fillers, an improvement in the physical properties of vulcanizates prepared therefrom is obtained.

We have now found that the addition of vinylchlorosilane-hydrogen sulfide reaction products (vinyl silthianes) to uncured rubber-filler mixtures also brings about improvements in the physical properties of the resulting vulcanizates. The improvements brought about by the vinyl silthianes are of the same nature as those obtained with vinylchlorosilane-glycol reaction products in accordance with the above-mentioned application. The beneficial effects of the vinyl silthianes are, however, of considerably greater magnitude. vinylchlorosilane-glycol reaction products are effective, to any appreciable degree, only in rubber-filler mixtures in which the filler is a specific silica or silicate product, especially calcium silicate or kaolin (clay), the vinyl silthi- "atent O Moreover, whereas the anes are eflfective in rubber-filler mixtures regardless of the type of filler contained therein. Of particular interest is the fact that the vinyl silthianes efiect improvements in the properties of vulcanizates containing carbon black and calcium carbonate, whereas the vinylchlorosilaneglycol reaction products have virtually no effect on the physical properties of vulcanizates containing these types of fillers.

The copending applications of Brooks et al., Serial No. 256,144, filed November 13, 1951 (now U. S. Patent 2,665,264), Boggs, Serial No. 261,361, filed December 12, 1951, and Ladd, Serial No. 266,099, filed January 11, 1952, are all based upon the discovery that the physical properties of rubber-filler vulcanizates are improved by the use therein of fillers which have been pre-treated, or are treated during intermixture with the elastomer, with certain organohalosilanes. The improvements obtained by the use of the thus-treated fillers are the same as those obtained by the addition of a reaction product of the silane and a polyhydric alcohol directly to a rubber-filler mixture in the manner disclosed in the above-identified Brooks et a1. application Serial No. 250,788. It has heretofore been concluded from this similarity of results that the silane-polyhydric alcohol reaction product reacted with the filler in the elastomer-filler mixture and thereby efiected a beneficial change in the reinforcing characteristics of the filler, similar to that which is obtained when the filler was treated with an organohalosilane prior to its addition to the rubber. Although we do not wish to be limited to any theory in the explanation of the results of our invention, it appears that the reaction of our vinyl silthianes in a rubber-filler mixture is generally similar to that of the silane-polyhydric alcohol reaction products.

The vinylchlorosilanes which we employ in making our silthianes are those in which all four valences of the silicon are satisfied by vinyl and chloro only.

In accordance with our invention We first react the 2,756,220 Patented July 24, 1956 vinylchlorosilane with hydrogen sulfide. This reaction is accompanied by liberation of an amount of hydrogen chloride corresponding to the amount of chlorine in the vinylchlorosilane and chemical attachment of the silicon atom to one, two or three sulfur atoms, depending upon the number of chlorine atoms originally present in the vinylchlorosilane.

For example when vinyltrichlorosilane is employed, the product of the reaction with the hydrogen sulfide contains the recurring unit structure I and analysis of the product shows that its content of carbon, hydrogen, silicon and sulfur responds to the empirical formula CH2=CHSiS3 z. Each of the dangling valences attached to sulfur in the foregoing unit structure is in turn attached to another silicon atom to which is attached a vinyl group.

In a typical method of preparing the reaction product of our invention, hydrogen sulfide in gaseous form is bubbled through a liquid mixture containing the vinylchlorosilane and a hydrogen chloride acceptor, preferably pyridine. It is preferable that an inert solvent for the reactants and for the vinylchlorosilane-hydrogen sulfide reaction product be present in the reaction vessel. Benzene is especially suitable as a solvent. An amount of hydrogen chloride acceptor should be used which is at least sufiicient to combine with all of the hydrogen chloride evolved during the reaction. We prefer to effect reaction by heating the solution of the vinylchlorosilane, hydrogen chloride acceptor, and inert solvent under reflux conditions, and to bubble the hydrogen sulfide gas through the solution while it is being refluxed. If desired, any suitable means for obtaining intimate contact between the hydrogen sulfide gas and the liquid reaction mixture can be provided. As the reaction proceeds the reaction product of the hydrogen chloride acceptor and the liberated hydrogen chloride is of course formed and usually separates out as a precipitate. When the reaction is complete, as is indicated by cessation of absorption of hydrogen sulfide, the reaction product is recovered from the reaction mixture in any suitable manner. It is noteworthy that the hydrogen sulfide selectively reacts with the chlorine in the vinylchlorosilane so as to replace chlorine with sulfur and that almost no reaction of hydrogen sulfide across the double bonds of the vinyl groups takes place.

The following example illustrates the preparation of one of our vinyl silthiane reaction products in more detail.

EXAMPLE I Six hundred grams of vinyltrichlorosilane and 960 grams of pyridine are dissolved in 1600 ml. of benzene. The mixture is then heated to reflux temperature and hydrogen sulfide is bubbled therethrough. As the reaction proceeds a heavy crystalline mass of pyridine hydrochloride forms. Introduction of the hydrogen sulfide is continued until its reaction with the silane ceases (as judged from bubble tubes for hydrogen sulfide located at the entrance to and exit from the reaction vessel).

When the hydrogen sulfide is no longer absorbed in the reaction mixture, the pyridine hydrochloride is filtered out and the filter cake washed in benzene. The wash fluid and the filtrate are then combined and the low-boiling fractions thereof removed by distillation at low pressure (30 mm.) and low temperature. The temperature is raised, during the course of the distillation, from C. at the start to C. at the finish.

The residue in the reaction vessel is the reaction prodnot of our invention. It is a viscous liquid at 125 C. and

a waxy solid at room temperature. It hydrolyzes in moist air, smells strongly of hydro-gen sulfide, dissolves almost Completely in xylene and dioxa lq and swells slightly. in

paraffin hydrocarbons.

Analysis .of the vinyltrichlorosilane-hydrogen sulfide reaction product indicates the unit structure is V CH2=.CHSiS3 2 The analytical dat'a'are summarized in the following ta- The yield of reaction product is 344 grams, comparedto a theoretical yield of 384 grams.

The reaction products of divinyldichlorosilane, or triyinylchlorosilane, and hydrogen sulfide are prepared in similar fashion.

. The vinyl silthianes of our invention are incorporated with elas'tomer-filter blends in any suitablemanner, .usually .by adding them to the elastorner-filler mixture and incorporating. them thoroughly therewith in standard rubber mixing equipment, such as the open rubber mill or an internal mixer such as a Banbury mixer. It is conceivable that the filler might be pretreated with the vinyl silthiane rea tion products ,of our invention, for example with'a solution thereof in a solvent medium, prior to'incorporation of the tiller into the elastomer. However, it is not likely that this method would offer any substantial advantage over pre-treatment of the filler with the vinylchlorosilane d re t y- As the vinyl silthiane is intermixed with the blend 'of elastomer' and filler, hydrogen sulfide is released. Part of this hydrogen sulfide is absorbed by the elastomer and the remainder 'is released into the surroundingatmosphere. it is therefore preferable that provision be made at the mixing apparatus to remove hydrogen sulfide vapors. Ex- 1.3 515 hoods above the ram used at the top of internal mixers of the Banbury type are in common use and provide adequate means for removal of the hydrogen sulfide vapors.

For good results it is essential that thernixture of elastomer, filler and vinyl silthiane be heated at an elevated temperature in order to effect the desired reaction between the "vinyl silthiane and the filler. Temperatures of the order of 250 to 400 F. are necessary to effect this reaction at a practical speed. We much prefer to mill orrnasticate the mixture while heating it to such temperatures. The desired mastication and high temperature are easily obtained in the ordinary Banbury mixer. Following completion of the reaction between the silthiane and the filler, as is evidenced by cessation of liberation of hydrogen sulfide, the mixture is cooled to a temperature substantially below 250 F., say to 150 F., or to any other temperature at which undesired reaction of the vulcanizing ingredients will not take place. Thereupon a suitable amount of sulfur and suitable proportions of vulcanization accelerators are intimately admixed at such low temperatures.

If a softener is to be used in the formulation, it is often desirable to have it present during the reaction between the silthiane and the filler. i

The resulting mixture is then shaped and vulcanized in the conventional manner. 7

Natural rubber or any synthetic rubber containing at least 25% of combined butadiene can be used in the practice of our invention. The synthetic rubber can be either ubb phlyheta ehe. the h mope mer o be diene, or a copolyrner of 25% or more of buta'diene c0- polymerized with up to of any suitable copolyrnerizable monomer such as styrene, acrylonitrile, esters of acrylic acid such as methyl acrylate or ethyl acrylate, esters of methacrylic acid such as methyl methacrylate, and the like. The rubber used can be classed as a sulfur-vulcanizable conjugated diolefin polymer rubber. 7

Any filler commonly used in rubber compounding can be used in the practice of our invention. Examples are the precipitated hydrated silicas, precipitated hydrated calcium silicates, any of the clays commonly used as rubber fillers, diatomaceous earth, titanium dioxide, aluminum oxide, carbon black, calcium carbonate, etc. It is demonstrated in the following examples that the process of our invention causes an increase in the tensile strength of vulcanizates, generally a reduction'in their permanent set, an increase in their modulus, and a reduction in their torsional hysteresis. The extent of these changes in the physical properties varies to a considerable degree depending on the filler employed in the vulcanizate. For example, although the treatment of our invention in general significantly improves the hot tensile strength ofvulcanizates, it may be accompanied by slight impairment of room temperature tensile strength when hydrated precipitated silicas, hydrated precipitated calcium silicates, or aluminum oxide are employed as fillers.

The amount of the vinylchlorosilane-hydrogen sulfide reaction product employed in the elastomer-filler mixture can vary widely. Generally speaking however it will usually-range from 0.5% to 10% of the filler weight. More commonly it will range from 1 to 5% of the filler weight. As, may be anticipated, stocks filled with fine particle fil lers require a greater amount of vinyl silthiane than do stocks filled with large particle fillers.

The following examples illustrate the utilization of our vinylchlorosilane-hydrogen sulfide reaction products in elastomer-filler mixers and the improvements in representative physical properties thereby obtained. All parts are by weight.

" EXAMPLE II This example illustrates the improved reinforcing properties imparted to fillers by the reaction products of our invention. A portion of the silthiane product of Example I was incorporated in a GR-S stock containing .I-li-Sil silica as the filler. Hi-Sil silica is a precipitated hydrated silica which has a particle size of about 200 Angstrom units, a surface area of square meters per gram, and a degree of hydration of 10.7% of moisture. For com.- parison purposes a stock containing diethylene glycol was prepared at the same time. The use of diethyleneglycol for improving the properties of silica-filled stocks is disclosed in U. S. patent to Pechukas 2,5 64,992. The formulations were as follows:

The method of mixing n o ed blend n he C R- h cou sin the -Sfli he stear a id n the reactionproduct or the -diethyleneglycol in the cold nd m l the m e f 10 m u e at 300 F- Th remaining ingredients were then added on a 150 F. mill.

The hot milling was carried out in order to give the silane-Hzs r ction pr duct, us d i sto k I-A opportunity to, r a t w th h fi l r, e est ock sme led ethydr GR-S 100 of the cured stocks were as indicated in the following table.

Table I Room Temperature 212 F. 280 F.

Stock Duro- Set Modulus, Tors. meter Tensile Elong. at 300% Tensile Hyst.

Break Strain I-A 61 2, 580 550 37 1,050 915 .15 16 I-B 63 2, 520 320 16 1, 850 1, 140 07 about 300 Angstrom and containing about 13-19% water of hydration. Suprex Clay, which was added to stocks III-C and III-D, is a kaolin having plate-like particles of a wide distribution of sizes averaging approximately 5000 Angstrom units andcontaining 14.1% of water of hydration. Celite 505 is an amorphous diatomaceous earth having an average particle size of approximately 5 microns. Titanox is an anatase crystal type titanium dioxide having a particle size of less than 0.5 micron. Alumina C-730 is a hydrated aluminum oxide having a 36% water of hydration and an average particle size of less than 0.6 micron.

The stocks were processed in the same manner as were the stocks in Example II. They were then presscured for 45 minutes at a temperature of 292 F. The physical properties of the resultant vulcanizates are listed in the following table.

Table II Room Temperature 212 1?. 280 F.

Stock (R. P.=Yinytrichlorosilane-H S K680151011 fl c Duro- Percent Modulus, TOIS. meter Tensile Elong. Set at 300% St. Tensile Hyst. Break HI-A (Silene EF) 54 2, 290 620 35 675 760 099 III-B (Silene EF-i-R. P.) 59 2, 020 450 16 1, 140 860 079 III-O lay) 55 1, 470 560 34 720 425 109 III-D (Clay+R P 55 2, 040 310 11 l, 875 1, 050 071 III-E (D atomaecous 65 830 260 12 645 285 089 III-F (D atomaceous Earth-l-R P 66 1, 370 250 7 1, 180 640 059 III-G (Titanium Ox de) 53 2, 240 680 26 360 355 .091 III-H (Titamum Ox1de+R. P,) 58 2, 460 470 14 1,180 840 057 III-I (Aluminum Oxide) 46 1, 690 670 300 180 072 III-.T (Aluminum Oxlde+R. P.) 52 1, 400 480 13 800 495 064 1 200% strain.

The improvements in hot tensile (212 F.), set at break,

torsional hysteresis, and modulus imparted by our reaction product, are apparent from the data shown in Table I.

Although our invention is not limited to use with any particular class of fillers, we find that particularly good results are obtained with silica, silicate, titanium dioxide,

and aluminum oxide fillers. The following example illustrates the improvement obtained by treatment of a large variety of these fillers with our reaction product.

EXAMPLE III GR-S stocks were prepared in accordance with the formulations listed below. Equal volumes of fillers were used.

STOCKS l'II-A 111-3 111-0 III-D III-E III-F III-G III-H III-I III-I Reaction productL Silene EF" 58 Suprex Clay Celite 505" 1 Vinyltrlchlorosilane-hydrogen sulfide reaction product (made as in Example I).

Silene E which was added to stocks LIL-A and HI-B is a hydrated calcium silicate having a particle size of following table. For comparison a stock containing no reaction product is also included.

Table 111 Room Temperature Stock 212 F. 280 F.

Duro- Percent Mod, Tens. TIL meter Tensile Elong. Set at 300% Bk. St.

Clay (control) 60 1, 740 570 36 915 475 1 G1ay+viny1tnehlorosllane glycol reaction product 62 1, 610 440 21 1, 350 775 07 The stocks in Table III were compounded similarly to those. in Table II except that 3.0 parts of sulfur was used ratherthan 2.5 parts. When the data in Table III'are compared with those for clay in Table II, the superiority of our treating agent is immediately evident. The tensile, percent set at break and modulus data are particularly illustrative of this fact.

carbo black emp y was a d um p ces in channel black. Witcarb R-l2 is a precipitated calcium carbonate having a particle size of approximately 0.15 mi ron r The stocks were press-cured-by heating with steam at 292 F. for minutes. The physical properties of the resultant vulcanizates are listed in the following table.

Table IV Room Temperature Stock 212 F. 280 F.

Duro- Percent Mod., Tens. '1. H. meter Tensile Elong. Set at 300% Bk. St.

W7C (Oarbonblaelg) 65 3, 150 450 11 1, 575 1, 120 19 IV-D (Carbon black+reactlon product) 65 3, 510 440 12 2, 050 1,320 .09 1'VA (Calcium carbonate) 1, 530 640 30 330 256 09 IV-B (Calcium carbonate-He- 7 action product) 52 1,840 620 30 560 397 .08

EXAMPLE V EXAMPLE IV 35 Four GR-S stocks were prepared in accordance with The use in GR-S of fillers treated in accordance with the process of our invention has been illustrated in Examples II, III and IV. In Table V are shown data on vulcanizates of two other copolymers of butadiene, viz., a butadiene-acrylonitrile copolymer (GR-A) and a butadiene-methylmethacrylate copolymer. Each vulcanizate contains clay (Suprex Clay) as a filler.

The stocks were compounded and processed similarly to the GRTS stocks in Examples II and III, except for slight modifications in acceleration.

Two parts of our vinyltrichlorosilane-hydrogen sulfide reaction product were used in the treated stocks. The

improvements in physical properties imparted by the process of our invention are evident from the data in Table V.

Table V Room Temperature Stock 212F. 280F;

Duro- Ten- Percent Modulus, Tens. T. Hyst. meter sile Elong. Set at 300% St.

B ea

Butadiene-Acrylonitrlle con taming:

clay 60 1, 720 420 23 1, 420 545 i 99$ clay+v1nyl-trlchloro-s1lane- Hrs reaction product 62 2, 040 250 11 2, 100 921 72 Bntadiene-methylmethacrylate containing:

clay 53 95c 400 30 720 255 13 clay-vinyl-trlchloro-sllane- HIS reaction product 1, 090 410 24 875 370 .109

1 Made as in Example'I.

the following formulations. The stocks were processed similarly to those in Example II.

Witcarb R-12. Reaction product Coumarone resin.

for rub her) Accelerators. Sulfur 1 Vinylttiehlorosilane-HzS reaction product (made as in Example I).

The products formed by the reaction of saturated organochlorosilanes with hydrogen sulfide, e. g., the reaction product of ,ethyltrichlorosilane and hydrogen sulfide, effect only minor improvements in the physical properties of the vulcanizates. 7 Although we prefer to use copolymers of butadiene as the rubber in the process of our invention,-natural rubber stocks may also'be used. For example, clay filled natural rubber vulcanizates prepared according to the process of our invention, although displaying only small improvements in tensile strength and torsional hysteresis, were improved in modulus from 1310 to 1760. The permanent set of the vulcanizate was reduced from 54% at break to 33%.

From the foregoing description many advantages of the present invention will be readily apparent to those skilled in the art. The principal advantage is that the present invention provides a simple and commercially feasible method of greatly improving the physical properties of synthetic rubber vulcanizates based on butadiene polymers and copolymers filled with the common fillers of the rubber industry. Another advantage is that the present invention makes it possible to prepare and market at relatively low cost a valuable new rubber chemical which can be used by rubber compounders in a way which does not require any extensive deviation from conventional compounding practices and which does not entail the use of special equipment. A marked advantage of our invention is that it enables considerable improvement in physical properties of vulcanizates containing such cheap and commonly available rubber fillers as carbon black and calcium carbonate which are not susceptible to improvement by treatment in accordance with the disclosures of the aboveidentified patent applications. Numerous other advantages of our invention will be apparent to those skilled in the art.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. The method which comprises commingling a sulfurvulcanizable conjugated diolefin polymer rubber, a filler, and from 0.5 to 10%, on the weight of the filler, of a vinyl silthiane, and heating the mixture at a temperature of at least 250 F. to eifect reaction between said vinyl silthiane and said filler, the said vinyl silthiane being the product of interaction of a vinylchlorosilane wherein the sum of the vinyl and chloro groups is equal to 4 with hydrogen sulfide passed in gaseous form into a solution at reflux temperature of said vinylchlorosilane, in the presence of a hydrogen chloride acceptor, to effect liberation of an amount of hydrogen chloride corresponding to the amount of chlorine in the vinylchlorosilane, whereby there is formed a vinyl silthiane consisting of vinyl groups, silicon atoms and sulfur atoms, each of said silicon atoms being chemically attached to vinyl groups and sulfur atoms, the sum of the number of vinyl groups and sulfur atoms to which each of said silicon atoms is attached being equal to 4.

2. The method which comprises commingling a sulfurvulcanizable conjugated diolefin polymer rubber, a filler, and from 0.5 to 10%, on the weight of the filler, of a vinyl silthiane, and heating the mixture at a temperature of at least 250 F. to eifect reaction between said vinyl silthiane and said filler, the said vinyl silthiane being the product of interaction of vinyltrichlorosilane with hydrogen sulfide passed in gaseous form into a solution at reflux temperature of said vinyltrichlorosilane, in the presence of a hydrogen chloride acceptor, to effect liberation of 3 moles of hydrogen chloride for each mole of vinyltrichlorosilane, whereby there is formed a vinyl silthiane having the recurring unit structure I each of the dangling valences attached to sulfur in said unit structure being in turn attached to another silicon atom to which is attached a vinyl group, said vinyl silthiane responding to the empirical formula and being a waxy solid 21 room temperature and a viscous liquid at 125 C.

3. The method which comprises commingling a sulfurvulcanizable conjugated diolefin polymer rubber, a filler, and from 0.5 to 10%, on the weight of the filler, of a vinyl silthiane, and heating the mixture while masticating it at a temperature of from 250 to 400 F. to effect reaction between said vinyl silthiane and said filler, the vinyl sithliane being the product of interaction of vinyltrichlorosilane with hydrogen sulfide passed in gaseous form into a solution at reflux temperature of vinyltrichlorosilane, in the presence of a hydrogen chloride acceptor, to efiect liberation of 3 moles of hydrogen chloride for each mole of vinyltrichlorosilane, whereby there is formed a vinyl silthiane having the recurring unit structure each of the dangling valences attached to sulfur in said unit structure being in turn attached to another silicon atom to which is attached a vinyl group, said vinyl silthiane responding to the empirical formula and being a waxy solid at room temperature and a viscous liquid at C.

4. A vulcanizate of a mixture of a sulfur-vulcanizable conjugated diolefin polymer rubber, a filler, and from 0.5 to 10%, on the weight of said filler, of a vinyl silthiane, said vinyl silthiane being the product of interaction of a vinylchlorosilane wherein the sum of the vinyl and chloro groups is equal to 4 with hydrogen sulfide passed in gaseous form into a solution at reflux temperature of said vinylchlorosilane, in the presence of a hydrogen chloride acceptor, to effect liberation of an amount of hydrogen chloride corresponding to the amount of chlorine in the vinylchlorosilane, whereby there is formed a vinyl silthiane consisting of vinyl groups, silicon atoms and sulfur atoms, each of said silicon atoms being chemically attached to vinyl groups and sulfur atoms, the sum of the number of vinyl groups and sulfur atoms to which each of said silicon atoms is attached being equal to 4.

5. A vulcanizate of a mixture of a sulfunvulcanizable conjugated diolefin polymer rubber, a filler, and from 0.5 to 10%, on the weight of said filler, of a vinyl silthiane, said vinyl silthiane being the product of interaction of vinyltrichlorosilane with hydrogen sulfide passed in gaseous form into a solution at reflux temperature of said vinyltrichlorosilane, in the presence of a hydrogen chloride acceptor, to effect liberation of 3 moles of hydrogen chloride for each mole of vinyltrichlorosilane, whereby there is formed a vinyl silthiane having the recurring unit structure each of the dangling valences attached to sulfur in said unit structure being in turn attached to another silicon atom to which is attached a vinyl group, said vinyl silthiane responding to the empirical formula References Cited in the file of this patent UNITED STATES PATENTS Moody Sept. 11, 1951 Sears et a1. Dec. 11, 1951 Prentiss et al. Ian. 15, 1952 

1. THE METHOD WHICH COMPRISES COMMUNIGLING A SULFURVULCANIZABLE CONJUGATED DIOLEFIN POLYMER RUBBER, A FILLER, AND FROM 0.5 TO 10%, ON THE WEIGHT OF THE FILLER, OF A VINYL SILTHIANE, AND HEATING THE MIXTURE AT A TEMPERATURE OF AT LEAST 250* F. TO EFFECT REACTION BETWEEN SAID VINYL SILTHIANE AND SAID FILTER, THE SAID VINYL SILTHIANE BEING THE PRODUCT OF INTERACTION OF VINYLCHLOROSILANE WHEREIN THE SUM OF THE VINYL AND CHLORO GROUPS IS EQUAL TO 4 WITH HYDROGEN SULFIDE PASSED IN GASEOUS FORM INTO A SOLUTION AT REFLUX TEMPERATURE OF SAID VINYLCHLOROSILANE, IN THE PRESENCE OF A HYDROGEN CHLORIDE ACCEPTOR, TO EFFECT LIBERATION OF AN AMOUNT OF HYDROGEN CHLORIDE CORRESPONDING TO THE AMOUNT OF CHLORINE IN THE VINYLCHLOROSILANE, WHEREBY THERE IS FORMED A VINYL SILTHIANE CONSISTING OF VINYL GROUPS, SILICON ATOMS AND SULFUR ATOMS, EACH OF SAID SILICON ATOMS BEING CHEMICALLY ATTACHED TO VINYL GROUPS AND SULFUR ATOMS, THE SUM OF THE NUMBER OF VINYL GROUPS AND SULFUR ATOMS TO WHICH EACH OF SAID SILICON ATOMS IS ATTACHED BEING EQUAL TO
 4. 